EP1679532A1 - Optical element having antireflection structure, and method for producing optical element having antireflection structure - Google Patents

Optical element having antireflection structure, and method for producing optical element having antireflection structure Download PDF

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Publication number
EP1679532A1
EP1679532A1 EP04793248A EP04793248A EP1679532A1 EP 1679532 A1 EP1679532 A1 EP 1679532A1 EP 04793248 A EP04793248 A EP 04793248A EP 04793248 A EP04793248 A EP 04793248A EP 1679532 A1 EP1679532 A1 EP 1679532A1
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EP
European Patent Office
Prior art keywords
antireflection structure
mold
optical element
press
molded
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04793248A
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German (de)
English (en)
French (fr)
Inventor
Makoto Matsushita Electric Ind. Co Ltd UMETANI
Yoshiyuki Matsushita Electr. Ind.Co.Ltd SHIMIZU
Yoshiharu Matsushita Electr.Ind. Co Ltd YAMAMOTO
Michihiro Matsushita Electr.Ind.Co. Ltd YAMAGATA
Yasuhiro Matsushita Electr. Ind.Co Ltd. TANAKA
Hiroshi Matsushita Electr. Ind. Co. Ltd YAMAGUCHI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003369522A external-priority patent/JP2005132660A/ja
Priority claimed from JP2003370946A external-priority patent/JP2005132679A/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP1679532A1 publication Critical patent/EP1679532A1/en
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/003—Light absorbing elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • C03B11/08—Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/082—Construction of plunger or mould for making solid articles, e.g. lenses having profiled, patterned or microstructured surfaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • C03B11/08—Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/084—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor
    • C03B11/086—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor of coated dies
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/02—Press-mould materials
    • C03B2215/08—Coated press-mould dies
    • C03B2215/10—Die base materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/02—Press-mould materials
    • C03B2215/08—Coated press-mould dies
    • C03B2215/14—Die top coat materials, e.g. materials for the glass-contacting layers
    • C03B2215/16—Metals or alloys, e.g. Ni-P, Ni-B, amorphous metals
    • C03B2215/17—Metals or alloys, e.g. Ni-P, Ni-B, amorphous metals comprising one or more of the noble meals, i.e. Ag, Au, platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/40—Product characteristics
    • C03B2215/41—Profiled surfaces
    • C03B2215/412—Profiled surfaces fine structured, e.g. fresnel lenses, prismatic reflectors, other sharp-edged surface profiles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to an optical element having an antireflection structure, and a method for producing the element.
  • the present invention relates to an optical element having an antireflection structure and being formed with multicomponent glass, and a method for producing the same.
  • the proposed antireflection structure has very fine concavities and convexities having an aspect ratio of 1 or more at sub-micron pitches.
  • micromachiningmethodby dry-etching process has been proposed.
  • JP62-28091B discloses that WC-based cemented carbide or cermet is used as a mold material, and the surface of a mold produced with this mold material is coated with a noble metal-based protective film. Then, using the mold having such a structure, it is possible to mass-produce optical elements by press-molding.
  • a carbon film having a thickness of 10 nm or less is formed on a surface having an optical function of the main body of the mold made of boron nitride, chromium nitride, chromium carbide, chromium oxide, silicon carbide, carbon, platinum or cemented carbide so as to provide good releasing properties with respect to glass.
  • the optical material that can be used is limited. That is to say, the optical material that can be used is limited to quartz glass or the like, and multicomponent glass or resin, which are used for optical devices that are designed with various optical constants, cannot be used. Therefore, when it is attempted to produce an optical element having an antireflection structure by micromachining method by dry-etching process, an optical element having an antireflection structure having a large aspect ratio cannot be obtained, because necessary selectivity cannot be obtained. Furthermore, since the repeatability of etching is low, the yield is reduced, mass productivity is lowered, and consequently the production cost is increased significantly.
  • a pressing surface of the mold When producing an optical element having an antireflection structure by press-molding, a pressing surface of the mold has to have an inverse shape of the optical element. However, it may be difficult to form an inverse shape, depending on the shape of the optical element. For example, in the case of a microlens array, in general, a cylinder-shaped resist pattern is formed on a substrate and then heated and softened, and a lens shape is formed by surface tension, and then the substrate is etched by dry-etching. However, by such a method, it is easy to form a convex shape, but it is very difficult to form a concave shape used as a mold.
  • the antireflection structure is formed with multicomponent glass and has a plurality of cone-shaped or polygonal pyramid-shaped structures being arranged, and an aspect ratio of which is 1 or more.
  • one of the above objects is achieved by the following method for producing an optical element having an antireflection structure on its surface, the antireflection structure is formed with multicomponent glass and has a plurality of cone-shaped or polygonal pyramid-shaped structures being arranged, and an aspect ratio of which is 1 or more, the method has the steps of heating multicomponent glass material, press-molding a heated multicomponent glass material with a mold having a shape corresponding to the antireflection structure to be formed, and removing a molded multicomponent glass material from the mold before the material is cooled to a temperature at which no change of a shape of the material occurs.
  • a method for producing an optical element of the present invention it is possible to release a mold having an antireflection structure from a press-molded optical material without cooling, so that the thermal stress due to the difference in the thermal expansion coefficient between the mold having an antireflection structure and the press-molded optical material can be prevented from being generated, and thus the precision of the pattern transferred to the optical material can be increased.
  • an optical element having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • the method for producing the optical element having an antireflection structure of the present invention because the optical element is produced by press-molding using the mold having an antireflection structure, the optical element having an antireflection structure can be produced with high repeatability. As a result, the mass productivity is significantly improved, and therefore, the production cost can be decreased significantly.
  • FIG. 1 is a cross-sectional view showing a mold for press-molding an optical element having an antireflection structure in a first embodiment of the present invention.
  • FIG. 1 is a cross-sectional view showing a mold for press-molding an optical element having an antireflection structure in the first embodiment of the present invention.
  • reference numeral 1 denotes a quartz glass substrate of 20 mm ⁇ 20 mm ⁇ 5 mm. Quartz glass is a material that has excellent high temperature strength and heat resistance and whose surface is hardly roughened by dry-etching.
  • a cone-shaped antireflection structure 2 having a pitch of 0.15 ⁇ m and a height of 0.15 ⁇ m is formed, and the quartz glass substrate 1 in which this antireflection structure 2 is formed is used as a mold 3 having an antireflection structure.
  • FIG. 2A first, the surface (pressing surface) of the quartz glass substrate 1 was processed so as to be smooth by high precision grinding and polishing (Ra: about 2nm). Then, as shown in FIG. 2B, a Cr film 20 having a thickness of 0.1 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 1 that had been processed so as to be smooth by sputtering. Then, as shown in FIG. 2C, a PMMA resist 21 having a thickness of 0.3 ⁇ m was formed on the surface of the Cr film 20 by spin-coating. Then, as shown in FIG.
  • a cylinder-shaped pattern 22 made of the PMMA resist having a diameter of 0.15 ⁇ m was formed on the surface of the Cr film 20 at a pitch of 0.15 ⁇ m by EB (electron beams) lithography.
  • EB electron beams
  • a cylinder-shaped pattern made of Cr corresponding to the antireflection structure 2 was formed as a mask on the surface (pressing surface) of the quartz glass substrate 1 by wet-etching the Cr film 20 (Cr mask 23).
  • This Cr mask 23 was formed in an array with a pitch of a wavelength to be used or less. Then, as shown in FIG. 2F, the quartz glass substrate 1 in which the cylinder-shaped Cr mask 23 was formed was placed in a RF dry-etching apparatus and the surface of the quartz glass substrate 1 was etched with CHF 3 + O 2 gas. Thus, the Cr mask 23 also was etched little by little together with the quartz glass substrate 1, and the width thereof was reduced. Then, the surface of the substrate was etched until the Cr mask 23 was no longer present, so that a cone-shaped antireflection structure 2 with a pitch of 0.15 ⁇ m and a height of 0.15 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 1.
  • the surface was little rough after the etching, and the surface roughness was substantially equal to that of a polished surface.
  • an Ir-Rh alloy film having a thickness of 0.05 ⁇ m for protecting the surface was formed by sputtering on the surface (pressing surface) of the quartz glass substrate 1 provided with the cone-shaped antireflection structure 2. In this manner, the mold 3 having an antireflection structure was obtained.
  • a lower mold 4 has the following structure. As shown in FIG. 1, a recess 4a of 15 mm ⁇ 15 mm ⁇ 0.5 mm is formed in the central portion of a WC-based cemented carbide of 20 mm ⁇ 20 mm ⁇ 5 mm, and an Ir-Rh alloy film having a thickness of 0.5 ⁇ m for protecting the surface is formed on the surface provided with the recess 4a by sputtering.
  • FIG. 3 shows a process sequence of a process for molding an optical element having an antireflection structure in the first embodiment of the present invention.
  • FIG. 4 shows a process sequence of a method for press-molding the optical element having an antireflection structure in the first embodiment of the present invention.
  • the mold 3 having an antireflection structure serving as an upper mold 6 was fixed on an upper head 5 of a molding machine covered with a chamber 15, and the upper mold 6 was heated to a predetermined temperature (590°C in this embodiment) together with a press stage 8. Moreover, a preheated stage 7 also was heated to 590°C.
  • the above-described lower mold 4 was used as a lower mold 10, and crown based borosilicate glass (glass transition point (Tg): 501°C, deformation point (At): 549°C) of 15 mm ⁇ 15 mm ⁇ 1.0 mm, which was an optical material 11, was placed on the lower mold 10, and the lower mold 10 on which the optical material 11 was placed was put in the molding machine from a mold inlet 12 of the chamber 15, and heated in the preheated stage 7 that was set to 590°C for 3 minutes.
  • a releasing agent 16 containing fine particles of carbon (C) for mold release was applied onto the surface of the optical material 11 (see FIG. 4A).
  • the lower mold 10 provided with the optical material 11 was transported from the preheated stage 7 to the press stage 8 that also was set to 590°C. Then, a cylinder 13 was lowered so as to press the optical material 11 with the upper mold 6 that also was set to 590°C and fixed to the upper head 5 at a pressure to be applied of 1000 N for 3 minutes (see FIGS. 4A and 4B). Then, the cylinder 13 was lifted without being cooled (at the temperature unchanged) so that the upper mold 6 as well as the upper head 5 were lifted, and thus the upper mold 6 was released from the press-molded optical material 11 (see FIGS. 4B and 4C).
  • the upper mold 6 can be released without being cooled (at a high temperature unchanged) from the press-molded optical material 11, because the wettability thereof with the optical material 11 is poor.
  • oxide or metal the upper mold cannot be released without being cooled (at a high temperature unchanged), whereas with carbon (C) (or boron nitride (BN)), the wettability is very poor, so that the upper mold can be released without being cooled (at a high temperature unchanged) .
  • C carbon
  • BN boron nitride
  • the lower mold 10 provided with the press-molded optical material 11 was transported from the press stage 8 to a cooling stage 9 that was set to 300°C, and was cooled for 3 minutes there.
  • the upper mold 6 (mold 3 having an antireflection structure) from the press-molded optical material 11 without cooling, so that the thermal stress due to the difference in the thermal expansion coefficient between the upper mold 6 (mold 3 having an antireflection structure) and the press-molded optical material 11 can be prevented from being generated, and thus the precision of the pattern transferred to the optical material 11 can be increased.
  • the optical element 17 having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • the optical element 17 is produced by press-molding using the mold 3 having an antireflection structure, the optical element 17 having an antireflection structure can be produced with high repeatability. As a result, the mass productivity is significantly improved, and therefore, the production cost can be decreased significantly.
  • quartz glass is used as the mold material that has excellent high temperature strength and heat resistance and whose surface is hardly roughened by dry-etching.
  • the present invention is not limited to quartz glass as the mold material, but for example, mold materials in which a SiO 2 film or a Si film is formed on silicon, a Ni alloy, or cemented carbide may be used.
  • crown based borosilicate glass is used as the optical material 11.
  • the present invention is not limited to crown based borosilicate glass as the optical material, and multicomponent glass or resin can be used.
  • multicomponent glass include aluminosilicate glass, flint glass and phosphate glass.
  • resin include acryl, fluorine-containing resin, polyethylene, and polyolefin. Since an antireflection structure is formed by molding, even if multicomponent glass or resin is used as the optical material 11, an optical element having an antireflection structure having a large aspect ratio can be obtained.
  • an Ir-Rh alloy film is used as a thin film for protecting the surface.
  • the present invention is not limited to Ir-Rh alloy films as a thin film for protecting the surface.
  • films containing at least one metal selected from the group consisting of Pt, Pd, Ir, Rh, Os, Ru, Re, W and Ta can be used.
  • a cylinder-shaped Cr mask corresponding to the antireflection structure 2 is formed on the surface (pressing surface) of the quartz glass substrate 1.
  • the present invention is not limited to this structure.
  • a mask can be formed of a material such as Ni, Au or C, or a polygonal prismatic mask can be formed.
  • a resist is patterned into a cylindrical shape or a polygonal prismatic shape, using electron beam lithography, but a resist can be patterned into a cylindrical shape or a polygonal prismatic shape, using X-ray lithography or photolithography employing interference exposure.
  • a mask is formed into a cylindrical shape or a polygonal prismatic shape by wet-etching, but a mask can be formed into a cylindrical shape or a polygonal prismatic shape by dry-etching.
  • substantially the same mold as in the first embodiment was used as the mold for press-molding an optical element having an antireflection structure (see FIG. 1).
  • the mold for press-molding in this embodiment is different from the mold for press-molding in the first embodiment in the following point.
  • a carbon (C) film for mold release having a thickness of 0.05 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 1 provided with the cone-shaped antireflection structure 2, instead of forming an Ir-Rh alloy film for protecting the surface.
  • a releasing agent for mold release is not applied onto the surface of the optical material 11 to be press-molded.
  • a method for producing the optical element 17 having an antireflection structure, using the mold 3 having an antireflection structure and the lower mold 4, is the same as that in the first embodiment (see FIGS. 3 and 4) and therefore is not described further. Also with this embodiment, for the same reason as in the first embodiment, the upper mold 6 (mold 3 having an antireflection structure) can be released without being cooled from the press-molded optical material 11, and therefore the optical element 17 having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • a carbon (C) film for mold release is formed on the surface (pressing surface) of the quartz glass substrate 1 provided with the cone-shaped antireflection structure 2.
  • the thin film for mold release is not limited to a carbon (C) film, and for example, a boron nitride (BN) film may be used.
  • the same mold as in the first embodiment was used as the mold for press-molding the optical element 17 having an antireflection structure (see FIG. 1).
  • the process for molding the optical element 17 having an antireflection structure is substantially the same as that in the first embodiment.
  • the molding process in this embodiment is different from the molding process in the first embodiment in the following point.
  • the optical element 17 having an antireflection structure is molded while N 2 and CO 2 (10 vol. %) were introduced from an atmosphere gas inlet 18 of the chamber 15 to the inside of the molding machine.
  • the optical element 17 having an antireflection structure was molded under the same conditions while introducing only N 2 gas to the molding machine. Then, the releasing properties between the upper mold 6 (mold 3 having an antireflection structure) and the optical material 11 were poor, so that the upper mold 6 (mold 3 having an antireflection structure) could not be released from the press-molded optical material 11 without being cooled (at a temperature unchanged (590 °C)) after the optical material 11 was pressed. In this case, when the temperature was lowered to 400°C, the upper mold 6 came to be released from the press-molded optical material 11, and then the optical element 17 having an antireflection structure was taken out after being cooled in the cooling stage 9. Then, the surface was observed.
  • the upper mold 6 when N 2 and CO 2 (10 vol.%) are introduced to the molding machine, the upper mold 6 (mold 3 having an antireflection structure) can be released easily from the press-molded optical material 11 at the temperature that is used for press-molding.
  • the upper mold 6 (mold 3 having an antireflection structure) can be released from the press-molded optical material 11 without being cooled (at a high temperature unchanged) for the following reason.
  • CO 2 gas is adsorbed onto the surfaces of the optical material 11 and the mold, the CO 2 gas can be provided with the function of a releasing agent and a releasing film.
  • the optical element 17 having an antireflection structure is molded while introducing N 2 and CO 2 (10 vol.%) from the atmosphere gas inlet 18 of the chamber 15 to the molding machine.
  • the gas is not limited to such an atmosphere, and any atmospheres in which gas or atomized liquid containing carbon (C) or fluorine (F) in the constituent molecules is mixed in an inert gas such as nitrogen (N 2 ) or argon (Ar) can be used.
  • an inert gas such as nitrogen (N 2 ) or argon (Ar)
  • N 2 nitrogen
  • Ar argon
  • a plano-convex lens having a cone-shaped microstructure having a pitch of 0.15 ⁇ m and a depth of 0.15 ⁇ m on one surface that is a convex surface is produced as the optical element having an antireflection structure of the present invention.
  • FIG. 5 shows a process sequence schematically showing a method for producing the mold having an antireflection structure used in the fourth embodiment of the present invention.
  • the surface (pressing surface) of a cylindrical quartz glass substrate 25 having a thickness of 10 mm and a diameter of 5 mm that was to be formed into a mold for press-molding an optical element having an antireflection structure was processed so as to be concave, which is an inverse shape of a convex lens, by high precision grinding and polishing.
  • a PMMA resist 26 having a thickness of 0.5 ⁇ m that is a resist for X lithography was formed by spin-coating on the surface (pressing surface) of the concave quartz glass substrate 25.
  • a cone-shaped pattern made of the PMMA resist having a diameter of 0.15 ⁇ m and a height of 0.3 ⁇ m was formed at a pitch of 0. 15 ⁇ m on the surface (pressing surface) of the quartz glass substrate 25 as a mask 29 corresponding to an antireflection structure by moving a mask 28 for X-ray lithography highly precisely while irradiating X rays 27.
  • This mask 29 was formed in an array with a pitch of a wavelength to be used or less.
  • the quartz glass substrate 25 in which the mask 29 made of the PMMA resist was formed was placed in a RF dry-etching apparatus and the surface of the quartz glass substrate 25 was etched with CHF 3 + O 2 gas.
  • a cone-shaped antireflection structure 30 with a pitch of 0.15 ⁇ m and a height of 0.15 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 25.
  • an Ir-Rh alloy film having a thickness of 0.05 ⁇ m for protecting the surface was formed via a Cr film by sputtering on the surface (pressing surface) of the quartz glass substrate 25 provided with the cone-shaped antireflection structure 30. In this manner, the mold 31 having an antireflection structure was obtained.
  • a lower mold has the following structure.
  • An Ir-Rh alloy film having a thickness of 0.5 ⁇ m for protecting the surface is formed by sputtering on the surface of a cylindrical WC-based cemented carbide having a thickness of 10 mm and a diameter of 5 mm.
  • a method for producing the optical element (plano-convex lens) having an antireflection structure, using the mold 31 having an antireflection structure (upper mold) and the lower mold, is the same as that in the first embodiment (see FIGS. 3 and 4) and therefore is not described further.
  • the upper mold (mold 31 having an antireflection structure) can be released without being cooled from the press-molded optical material 11, and therefore the optical element (plano-convex lens) having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • the cone-shaped mask 29 corresponding to an antireflection structure is formed on the surface (pressing surface) of the quartz glass substrate 25.
  • the mask is not limited to this structure, and for example, a polygonal pyramid-shaped mask can be formed.
  • FIG. 6 is a cross-sectional view showing a master mold having an antireflection structure for producing a mold for press-molding an optical element having an antireflection structure in the fifth embodiment of the present invention.
  • reference numeral 51 denotes a quartz glass substrate of 20 mm ⁇ 20 mm ⁇ 5 mm. Quartz glass is a material that has excellent high temperature strength and heat resistance and whose surface is hardly roughened by dry-etching.
  • a cone-shaped antireflection structure 52 having a pitch of 0. 15 ⁇ m and a height of 0.15 ⁇ m is formed, and the quartz glass substrate 51 in which this antireflection structure 52 is formed is used as a master mold 53 having an antireflection structure.
  • FIG. 7A the surface (pressing surface) of the quartz glass substrate 51 was processed so as to be smooth by high precision grinding and polishing (Ra: about 2nm). Then, as shown in FIG. 7B, a Cr film 75 having a thickness of 0.1 ⁇ m was formed by sputtering on the surface (pressing surface) of the quartz glass substrate 51 that had been processed so as to be smooth.
  • a PMMA resist 76 having a thickness of 0.1 ⁇ m was formed on the surface of the Cr film 75 by spin-coating.
  • a cylinder-shaped pattern 77 made of the PMMA resist having a diameter of 0.15 ⁇ m was formed on the surface of the Cr film 75 at a pitch of 0.15 ⁇ m by EB (electron beams) lithography.
  • a cylinder-shaped pattern made of Cr corresponding to the antireflection structure 52 was formed as a mask on the surface (pressing surface) of the quartz glass substrate 51 by wet-etching the Cr film 75 (Cr mask 78). This mask was formed in an array with a pitch of a wavelength to be used or less.
  • the quartz glass substrate 51 in which the cylinder-shaped Cr mask 78 was formed was placed in a RF dry-etching apparatus and the surface of the quartz glass substrate 51 was etched with CHF 3 + O 2 gas.
  • the Cr mask 78 also was etched little by little together with the quartz glass substrate 51, and the width thereof was reduced.
  • the surface of the substrate was etched until the Cr mask 78 was no longer present, so that a cone-shaped antireflection structure 52 with a pitch of 0. 15 ⁇ m and a height of 0. 15 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 51.
  • an Ir-Rh alloy film having a thickness of 0.05 ⁇ m for protecting the surface was formed by sputtering on the surface (pressing surface) of the quartz glass substrate 51 provided with the cone-shaped antireflection structure 52. In this manner, the master mold 53 having an antireflection structure was obtained.
  • FIG. 8 shows a process sequence of a process for molding a replica mold having an antireflection structure in the fifth embodiment of the present invention.
  • FIG. 9 shows a process sequence of a method for molding the replica mold having an antireflection structure in the fifth embodiment of the present invention.
  • the master mold 53 having an antireflection structure serving as an upper mold 6 was fixed on an upper head 5 of a molding machine that was covered with a chamber 15 and to which N 2 gas was introduced from an atmosphere gas inlet 18, and the upper mold 6 was heated to a predetermined temperature (750°C in this embodiment) together with a press stage 8. Moreover, a preheated stage 7 also was heated to 750°C.
  • alkali-free glass 70 glass transition point (Tg): 625°C, deformation point (At) : 696°C
  • Tg glass transition point
  • At deformation point
  • 696°C deformation point
  • the lower mold 10 on which the high melting point glass 70 was placed was put in the molding machine from a mold inlet 12 of the chamber 15, and heated in the preheated stage 7 that was set to 750°C for 2 minutes.
  • a releasing agent 71 containing fine particles of boron nitride (BN) for mold release was applied onto the surface of the alkali-free glass 70 (see FIG. 9A).
  • the lower mold 10 provided with the alkali-free glass 70 that is a high melting point glass was transported from the preheated stage 7 to the press stage 8 that also was set to 750°C.
  • a cylinder 13 was lowered so as to press the alkali-free glass 70 with the upper mold 6 that also was set to 750°C and fixed to the upper head 5 at a pressure to be applied of 2000 N for 2 minutes (see FIGS. 9A and 9B).
  • the cylinder 13 was lifted without being cooled (at the temperature unchanged) so that the upper mold 6 as well as the upper head 5 were lifted, and thus the upper mold 6 was released from the press-molded alkali-free glass 70 (see FIGS. 9B and 9C).
  • the upper mold 6 can be released without being cooled (at a high temperature unchanged) from the press-molded alkali-free glass 70, because the wettability between the BN particles and the alkali-free glass 70 is poor.
  • the upper mold cannot be released without being cooled (at a high temperature unchanged), whereas with BN particles (or C particles), the wettability thereof with the alkali-free glass 70 is very poor, so that the upper mold can be released without being cooled (at a high temperature unchanged).
  • the press-molded alkali-free glass 70 remains on the lower mold 10.
  • the lower mold 10 provided with the press-molded alkali-free glass 70 that is a high melting point glass was transported from the press stage 8 to a cooling stage 9 that was set to 400°C, and was cooled for 2 minutes there.
  • the press-molded alkali-free glass 70 was taken from a mold outlet 14 of the chamber 15 together with the lower mold 10, the press-molded alkali-free glass 70 was removed from the lower mold 10, and then the releasing agent 71 was removed. Then, an Ir-Rh alloy film having a thickness of 0.05 ⁇ m for protecting the surface was formed by sputtering. Thus, a replica mold 72 having an antireflection structure was obtained (see FIG. 9C).
  • FIG. 10 is a cross-sectional view showing a mold for press-molding an optical element having an antireflection structure in the fifth embodiment of the present invention.
  • FIG. 11 shows a process sequence of a process for molding an optical element having an antireflection structure in the fifth embodiment of the present invention.
  • FIG. 12 shows a process sequence of a method for press-molding an optical element having an antireflection structure in the fifth embodiment of the present invention.
  • reference numeral 72 denotes the replica mold having an antireflection structure
  • the lower mold 54 has the following structure.
  • a recess 54a of 15 mm ⁇ 15 mm ⁇ 0.5 mm is formed in the central portion of a WC-based cemented carbide of 20 mm ⁇ 20 mm ⁇ 5 mm, and an Ir-Rh alloy film having a thickness of 0.5 ⁇ m for protecting the surface is formed on the surface provided with the recess 54a by sputtering.
  • the replica mold 72 having an antireflection structure serving as an upper mold 6 was fixed on an upper head 5 of a molding machine that was covered with a chamber 15 and to which N 2 gas was introduced from an atmosphere gas inlet 18, and the upper mold 6 was heated to a predetermined temperature (590°C in this embodiment) together with a press stage 8. Moreover, a preheated stage 7 also was heated to 590°C.
  • the above-described lower mold 54 was used as a lower mold 10, and crown based borosilicate glass (glass transition point (Tg): 501°C, deformation point (At): 549°C) of 15 mm ⁇ 15 mm ⁇ 1.0 mm was placed as an optical material 11 on the lower mold 10, and the lower mold 10 on which the optical material 11 was placed was put in the molding machine from a mold inlet 12 of the chamber 15, and heated in the preheated stage 7 that was set to 590°C for 3 minutes.
  • a releasing agent 16 containing fine particles of boron nitride (BN) for mold release was applied onto the surface of the optical material 11 (see FIG. 12A).
  • the lower mold 10 provided with the optical material 11 was transported from the preheated stage 7 to the press stage 8 that also was set to 590°C. Then, a cylinder 13 was lowered so as to press the optical material 11 with the upper mold 6 that also was set to 590°C and fixed to the upper head 5 at a pressure to be applied of 1000 N for 3 minutes (see FIGS. 12A and 12B). Then, the cylinder 13 was lifted without being cooled (at the temperature unchanged) so that the upper mold 6 as well as the upper head 5 were lifted, and thus the upper mold 6 was released from the press-molded optical material 11 (see FIGS. 12B and 12C).
  • the upper mold 6 can be released without being cooled (at a high temperature unchanged) from the press-molded optical material 11 for the same reason above.
  • the press-molded optical material 11 remains on the lower mold 10.
  • the lower mold 10 provided with the press-molded optical material 11 was transported from the press stage 8 to a cooling stage 9 that was set to 300°C, and was cooled for 3 minutes there.
  • the upper mold 6 master mold 53 having an antireflection structure
  • the upper mold 6 replica mold 72 having an antireflection structure
  • both a thermal stress due to the difference in the thermal expansion coefficient between the upper mold 6 (master mold 53 having an antireflection structure) and the press-molded alkali-free glass 70 and a thermal stress due to the difference in the thermal expansion coefficient between the upper mold 6 (replica mold 72 having an antireflection structure) and the press-molded optical material 11 can be prevented from being generated, and thus the deterioration of the precision of the pattern transferred to the master mold 53 having an antireflection structure, the replica mold 72 having an antireflection structure, and the optical material 11 in this order can be suppressed. Consequently, the optical element 67 having a highly precise antireflection structure without pattern dislocation over a large
  • the optical element 67 is produced by press-molding using the master mold 53 having an antireflection structure and the replica mold 72 having an antireflection structure, the optical element 67 having an antireflection structure can be produced with high repeatability. As a result, the mass productivity is significantly improved, and therefore the production cost can be decreased significantly.
  • quartz glass is used as the mold material that has excellent high temperature strength and heat resistance and whose surface is hardly roughened by dry-etching.
  • the present invention is not limited to quartz glass as the mold material, but for example, mold materials in which a SiO 2 film or a Si film is formed on silicon, a Ni alloy, or cemented carbide may be used.
  • crown based boronilicate glass is used as the optical material 11.
  • the present invention is not limited to crown based borosilicate glass as the optical material, and multicomponent glass or resin can be used.
  • multicomponent glass include aluminosilicate glass, flint glass and phosphate glass.
  • resin include acryl, fluorine-containing resin, polyethylene, and polyolefin. Since an antireflection structure is formed by molding, even if multicomponent glass or resin is used as the optical material 11, an optical element having an antireflection structure having a large aspect ratio can be obtained.
  • an Ir-Rh alloy film is used as a thin film for protecting the surface.
  • the present invention is not limited to Ir-Rh alloy films as a thin film for protecting the surface.
  • films containing at least one metal selected from the group consisting of Pt, Pd, Ir, Rh, Os, Ru, Re, W and Ta can be used.
  • a cylinder-shaped Cr mask corresponding to the antireflection structure 52 is formed on the surface (pressing surface) of the quartz glass substrate 51.
  • a mask can be formed of a material such as Ni, Au or C, or a polygonal prism-shaped mask can be formed.
  • a resist is patterned into a cylindrical shape or a polygonal prismatic shape, using electron beam lithography, but a resist can be patterned into a cylindrical shape or a polygonal prismatic shape, using X-ray lithography or photolithography employing interference exposure.
  • a mask is formed into a cylindrical shape or a polygonal prismatic shape by wet-etching, but a mask can be formed into a cylindrical shape or a polygonal prismatic shape by dry-etching.
  • substantially the same mold as in the fifth embodiment was used as the master mold having an antireflection structure for producing a mold for press-molding an optical element having an antireflection structure (see FIG. 6).
  • the master mold 53 having an antireflection structure in this embodiment is different from the master mold 53 having an antireflection structure in the fifth embodiment in the following point.
  • a carbon (C) film for mold release having a thickness of 0.05 ⁇ m was formed on the surface (pressing surface) of the quartz glass substrate 51 provided with the cone-shaped antireflection structure 52, instead of forming an Ir-Rh alloy film for protecting the surface.
  • a releasing agent for mold release is not applied onto the surface of the alkali-free glass 70 that is a high melting point glass to be press-molded.
  • substantially the same mold as in the fifth embodiment was used as the replica mold having an antireflection structure for press-molding an optical element having an antireflection structure (see reference numeral 72 in FIG. 10).
  • the replica mold 72 having an antireflection structure in this embodiment is different from the replica mold 72 having an antireflection structure in the fifth embodiment in the following point.
  • a carbon (C) film for mold release having a thickness of 0.05 ⁇ m was formed on the surface (pressing surface) of the press-molded alkali-free glass 70 that is a high melting point glass.
  • a releasing agent for mold release is not applied onto the surface of the optical material 11 to be press-molded.
  • a method for producing the replica mold having an antireflection structure for press-molding an optical element having an antireflection structure, using the master mold 53 having an antireflection structure, and a method for producing the optical element 67 having an antireflection structure, using the replica mold 72 having an antireflection structure and the lower mold 54 are the same as those in the fifth embodiment (see FIGS. 8, 9, 11 and 12) and therefore are not described further.
  • the optical element 67 having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • a carbon (C) film is formed as a thin film for mold release on the surface (pressing surface) of the quartz glass substrate 51 provided with the cone-shaped antireflection structure 52.
  • a carbon (C) film is formed as a thin film for mold release on the surface (pressing surface) of the press-molded alkali-free glass 70 that is a high melting point glass.
  • the thin film for mold release is not limited to a carbon (C) film, and for example, a boron nitride (BN) film may be used.
  • the same master mold as in the fifth embodiment was used as the master mold having an antireflection structure for press-molding an optical element having an antireflection structure (see FIG. 6).
  • substantially the same replica mold as in the fifth embodiment was used as the replica mold having an antireflection structure for press-molding an optical element having an antireflection structure (see reference numeral 72 in FIG. 10).
  • the replica mold 72 having an antireflection structure in this embodiment is different from the replica mold 72 having an antireflection structure in the fifth embodiment in the following point.
  • the replica mold 72 having an antireflection structure was produced (molded) while introducing N 2 and CO 2 (10 vol.%) from the atmosphere gas inlet 18 of the chamber 15 to the molding machine without applying a releasing agent for mold release onto the surface of the alkali-free glass 70 that is a high melting point glass to be press-molded.
  • the process for molding the optical element 67 having an antireflection structure in this embodiment is substantially the same as in the fifth embodiment.
  • the process for molding the optical element 67 having an antireflection structure in this embodiment is different from the process for molding the optical element 67 having an antireflection structure in the fifth embodiment in the following point.
  • the optical element 67 having an antireflection structure was molded while introducing N 2 and CO 2 (10 vol.%) from the atmosphere gas inlet 18 of the chamber 15 to the molding machine without applying a releasing agent for mold release onto the surface of the optical material 11 to be press-molded.
  • the production (molding) of the replica mold 72 having an antireflection structure and the molding of the optical element 67 having an antireflection structure with the replica mold 72 having an antireflection structure were performed while introducing only N 2 gas to the molding machine under the same conditions.
  • the releasing properties between the master mold 53 having an antireflection structure and the alkali-free glass 70 that is a high melting point glass and the releasing properties between the replica mold 72 having an antireflection structure and the optical material 11 were poor, so that the master mold 53 having an antireflection structure could not be released from the press-molded alkali-free glass 70 without being cooled (at the temperature unchanged (750 °C)) after the alkali-free glass 70 was pressed, and the replica mold 72 having an antireflection structure could not be released from the press-molded optical material 11 without being cooled (at the temperature unchanged (590 °C)) after the optical material 11 was pressed.
  • the master mold 53 having an antireflection structure came to be released from the press-molded alkali-free glass 70, and the replica mold 72 having an antireflection structure came to be released from the press-molded optical material 11, and then the optical element 67 having an antireflection structure was taken out after being cooled in the cooling stage 9. Then, the surface was observed.
  • an optical element pattern having an antireflection structure was formed precisely in the center, pattern dislocation becomes larger as being more apart from the center, and the optical element pattern having an antireflection structure was doubled in the vicinity of the periphery.
  • the master mold 53 having an antireflection structure and the replica mold 72 having an antireflection structure can be released easily from the press-molded alkali free-glass 70 and the press-molded optical material 11, respectively, at the temperature that is used for press-molding.
  • the master mold 53 having an antireflection structure and the replica mold 72 having an antireflection structure can be released from the press-molded alkali free-glass 70 and the press-molded optical material 11, respectively, without being cooled (at a high temperature unchanged) for the following reason.
  • the production (molding) of the replica mold 72 having an antireflection structure and the molding of the optical element 67 having an antireflection structure with the replica mold 72 having an antireflection structure are performed while introducing N 2 and CO 2 (10 vol. %) from the atmosphere gas inlet 18 of the chamber 15 to the molding machine.
  • the gas is not limited to such an atmosphere, and any atmospheres in which gas or atomized liquid containing carbon (C) or fluorine (F) in the constituent molecules is mixed in an inert gas such as nitrogen (N 2 ) or argon (Ar) can be used.
  • the same effect as above also can be obtained when the optical element 67 having an antireflection structure is molded while a gas obtained by passing a mixed gas of N 2 and CF 4 (10 vol.%) or N 2 gas through an ethylene glycol solution is introduced to the molding machine.
  • a microlens array with a convex shape of a pitch of 50 ⁇ m, a central height of 3 ⁇ m and a radius of curvature of 100 ⁇ m having a cone-shaped microstructure of a pitch of 0.15 ⁇ m and a height of 0.15 ⁇ m is produced as the optical element having an antireflection structure of the present invention.
  • FIG. 13 shows a process sequence of a process for producing a quartz microlens array on which the master mold having an antireflection structure used in the eighth embodiment of the present invention is based.
  • FIG. 14 shows a process sequence of a process for producing the master mold having an antireflection structure used in the eighth embodiment of the present invention.
  • FIG. 13A first, the surface of a quartz glass substrate 79 of 20 mm ⁇ 20 mm ⁇ 5 mm that was to serve as the master mold having an antireflection structure was processed so as to be smooth by high precision grinding and polishing (Ra: about 2nm). Then, as shown in FIG. 13B, a photoresist 80 having a thickness of 3 ⁇ m was formed by spin-coating on the surface of the quartz glass substrate 79 that had been processed so as to be smooth. Then, as shown in FIG.
  • a cylinder-shaped photoresist pattern 81 was formed by irradiating the surface of the quartz glass substrate 79 provided with the photoresist 80 with ultraviolet rays via a photomask provided with a circular pattern of a pitch of 50 ⁇ m and performing development, and removing an unexposed portion.
  • the entire substrate was heated at a temperature (200°C) at which the photoresist was melted, and heating for melting was performed until each cylinder-shaped photoresist was provided with a microlens shape by surface tension.
  • a semispherical photoresist pattern 82 was formed on the surface of the quartz glass substrate 79.
  • the quartz glass substrate 79 on which the semispherical photoresist pattern 82 was formed was cooled and then was placed in a RF dry-etching apparatus and the surface of the quartz glass substrate 79 was etched with CHF 3 + O 2 gas.
  • a microlens array 83 with a pitch of 50 ⁇ m and a height of 3 ⁇ m was formed on the surface of the quartz glass substrate 79, and a quartz microlens array 84 was obtained.
  • an antireflection structure was formed on the thus produced quartz microlens array 84 by the process shown in FIG. 14.
  • a PMMA resist 85 having a thickness of 0.5 ⁇ m that is a resist for X ray lithography was formed on the surface of the quartz microlens array 84 by spin-coating. Then, as shown in FIGS.
  • a cone-shaped pattern made of the PMMA resist having a diameter of 0.15 ⁇ m and a height of 0.3 ⁇ m was formed at a pitch of 0.15 ⁇ m on the surface of the quartz microlens array 84 as a mask 88 corresponding to an antireflection structure by moving a mask 87 for X-ray lithography highly precisely and developing while irradiating X rays 86.
  • This mask 88 was formed in an array with a pitch of a wavelength to be used or less.
  • the quartz microlens array 84 in which the mask 88 made of the PMMA resist was formed was placed in a RF dry-etching apparatus and the surface of the quartz microlens array 84 was etched with CHF 3 + O 2 gas.
  • a cone-shaped antireflection structure 89 with a pitch of 0.15 ⁇ m and a height of 0. 15 ⁇ m was formed on the surface of the quartz microlens array 84.
  • an Ir-Rh alloy film having a thickness of 0.05 ⁇ m for protecting the surface was formed via a Cr film by sputtering on the surface of the quartz microlens array 84 provided with the cone-shaped antireflection structure 89. In this manner, the master mold 90 having an antireflection structure was obtained.
  • a method for producing a replica mold having an antireflection structure for press-molding a microlens array as an optical element having an antireflection structure, using the master mold 90 having an antireflection structure, and a method for producing the microlens array as an optical element having an antireflection structure, using the replica mold having an antireflection structure and the lower mold are the same as those in the fifth embodiment (see FIGS. 8, 9, 11 and 12) and therefore are not described further.
  • the microlens array as an optical element having a highly precise antireflection structure without pattern dislocation over a large area can be molded repeatedly.
  • a cone-shaped mask corresponding to the antireflection structure is formed on the surface (pressing surface) of the quartz glass substrate 79.
  • the present invention is not limited to this structure.
  • a polygonal pyramid-shaped mask can be formed.
  • An optical element according to the present invention is suitable as a lens element, a mirror element and a prism element used for an imaging optical system such as a digital still camera or a video camera, a projection optical system such as a projector, an illumination optical system, and a laser optical system such as an optical pickup device or an optical scanning device, as a microlens array used for improving luminance of a liquid crystal display, and as a coupling microlens used in optical networking.

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EP04793248A 2003-10-29 2004-10-29 Optical element having antireflection structure, and method for producing optical element having antireflection structure Withdrawn EP1679532A1 (en)

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JP2003369522A JP2005132660A (ja) 2003-10-29 2003-10-29 無反射構造を有する光学素子の製造方法、及び当該方法により製造された無反射構造を有する光学素子
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PCT/JP2004/016147 WO2005040864A1 (ja) 2003-10-29 2004-10-29 反射防止構造体を有する光学素子、および反射防止構造体を有する光学素子の製造方法

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